CN110475605A - The manufacturing method of seperation film and seperation film - Google Patents

Abstract

Project to be solved by this invention is to provide the seperation film mainly formed by thermoplastic resin with high-permeability energy.The present invention relates to a kind of seperation films, and containing thermoplastic resin, the width in the gap of above-mentioned seperation film is 1nm or more and 1000nm hereinafter, the bent road rate in above-mentioned gap is 1.0 or more and 6.0 or less.

Description

The manufacturing method of seperation film and seperation film

Technical field

The present invention relates to seperation film and its manufacturing methods.

Background technique

In recent years, porosity seperation film is medical in the water treatment fields such as clean water treatment, drainage sunk well, blood purification etc. On the way, it is utilized in the various aspects such as field of food industry, battery separator, charged membrane, electrolyte membrane for fuel cell.

Cellulose-based resin is resistance to as the fungicide of chlorine system as having due to its hydrophilic through performance, being resistant to Chlorine performance, therefore be widely used as using water process with film as the porosity seperation film of representative.

For example, Patent Document 1 discloses the film by will be made of cellulose triacetate and solvent, non-solvent is former Liquid, which is discharged in the solidification liquid being made of solvent, non-solvent, water, separates it mutually, to obtain the technology of hollow fiber membrane.

Furthermore Patent Document 2 discloses a kind of ultrafiltration hollow fiber membranes, which is characterized in that hydroxy alkyl cellulose with The state of particle is adhered to hollow fiber membrane, the hydroxyalkylcellulose for the range that the most surface depth away from above-mentioned hollow fiber membrane is 1 μm The size of the particle of element is 5nm or more and 100nm or less.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2011-235204 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2015-157278 bulletin

Summary of the invention

Problems to be solved by the invention

It is asymmetric membrane by the hollow fiber membrane that technology documented by above-mentioned patent document 1 and patent document 2 obtains, Keep layer thin with the small separating layer in the aperture for undertaking separation function, but in order to obtain high water-permeability energy, exist be easy to generate it is scarce Fall into such project.On the other hand, if making to separate thickness to inhibit defect to generate, there are water permeabilities to reduce in this way Project.

The present invention is in view of the background of such prior art, and seperation film for having high water-permeability with offer etc. is as a purpose.

Means for solving the problems

The inventors of the present invention have made intensive studies in order to solve the above problems, as a result, it has been found that, by contain thermoplasticity The bent road rate in resin and gap is 1.0 or more and 6.0 seperation films below, and the width so as to provide in above-mentioned gap is With the seperation film of high water-permeability in 1nm or more and the micro-aperture field below 1000nm, so as to complete the present invention.

That is, the present invention has any composition below.

[1] a kind of seperation film, containing thermoplastic resin,

Above-mentioned seperation film has width for 1nm or more and the gap below 1000nm,

The bent road rate in above-mentioned gap is 1.0 or more and 6.0 or less.

[2] seperation film according to above-mentioned [1] has phase and above-mentioned gap shape by containing above-mentioned thermoplastic resin At co-continuous structure.

[3] seperation film according to above-mentioned [1] or [2] is obtained to MIcrosope image progress Fourier transformation In the curve for the figure that horizontal axis is wave number, the longitudinal axis is intensity, when being set as (a) by half-peak breadth, the very big wave number at peak be set as (b), institute The region that seperation film includes 0 < (a)/(b)≤1.5 is stated, the microscope figure seems with the gap of the seperation film The MIcrosope image taken in 10 times or more of width and the visual field of 100 times of length below as the square of side length.

[4] seperation film according to any one of above-mentioned [1]~[3], 50kPa, the film infiltration under the conditions of 25 DEG C are logical Amount is 0.05m³/m²/ h or more and 20m³/m²/ h or less.

[5] seperation film according to any one of above-mentioned [1]~[4], above-mentioned seperation film with a thickness of 1 μm or more and 1000 μm or less.

[6] seperation film according to any one of above-mentioned [1]~[5], above-mentioned seperation film are macaroni yarn shape.

[7] seperation film according to above-mentioned [6], the outer diameter of above-mentioned macaroni yarn shape be 100 μm or more and 5000 μm with Under.

[8] seperation film according to any one of above-mentioned [1]~[7], above-mentioned thermoplastic resin include to be selected from cellulose At least one kind of compound in ester, polyamide and polyester.

[9] seperation film according to above-mentioned [8], above-mentioned cellulose esters are cellulose-acetate propionate and/or acetate butyrate Cellulose.

[10] seperation film according to above-mentioned [8], above-mentioned polyamide are nylon 6 and/or nylon66 fiber.

[11] seperation film according to above-mentioned [8], above-mentioned polyester are polymer in poly lactic acid series and/or poly terephthalic acid Glycol ester.

[12] a kind of manufacturing method of seperation film, with following processes:

Resin melting process, by by 20 weight % or more and 90 weight % thermoplastic resin below and 10 weight % Above and 60 weight % structure-forming agents below are melted and are kneaded and modulate molten resin；

Molding procedure obtains membranaceous formed body and above-mentioned molten resin is discharged from discharge mouth mold；

Co-continuous structure formation process, it is below by 40 DEG C or more and 220 DEG C in above-mentioned molten resin or formed body Thermal inactive in liquid is formed by the 1st phase containing thermoplastic resin and the 2nd phase shape with above-mentioned 1st phase partially compatible At co-continuous structure；And

Process is dissolved out, by after above-mentioned co-continuous structure formation process and molding procedure, by the 2nd phase from above-mentioned formed body It dissolves out and forms gap.

[13] manufacturing method of the seperation film according to above-mentioned [12], above-mentioned thermoplastic resin are cellulose esters.

[14] manufacturing method of the seperation film according to above-mentioned [12] or [13], in above-mentioned molding procedure, by making Spinning head is used to form macaroni yarn as above-mentioned discharge mouth mold.

The effect of invention

Seperation film of the invention has the phase containing thermoplastic resin and gap, and gap is below with 1.0 or more and 6.0 Bent road rate.It may be said that bent road rate is closer to 1, then linearity is higher, and flow path length is shorter.In this way, by bent road rate it is small to Flow path length shortens, and water is readily flowed, therefore can get high water-permeability.

Detailed description of the invention

Fig. 1 is the sectional view for schematically showing the co-continuous structure of seperation film of the invention.

Specific embodiment

The inventors of the present invention have high water-permeability to the above subject, the seperation film containing thermoplastic resin is goed deep into Research, as a result, by the bent road rate in above-mentioned gap be 1.0 or more and 6.0 films below, successfully solve such project.

I.e. the present invention is a kind of seperation film, which is characterized in that containing thermoplastic resin, the width in the gap of above-mentioned seperation film For 1nm or more and 1000nm hereinafter, the bent road rate in above-mentioned gap is 1.0 or more and 6.0 or less.

Hereinafter, being illustrated to seperation film and resin combination of the invention.

1. seperation film

The composition summary of (1-1) seperation film

Seperation film of the invention contains thermoplastic resin.In addition, seperation film has the phase containing thermoplastic resin and gap.

Seperation film of the invention preferably comprises thermoplastic resin (A) as principal component.Here so-called principal component refers to composition Among the whole components of the resin combination of seperation film, most ingredients for including by weight.The thermoplastic resin in seperation film Ratio shared by rouge (A) is preferably 50 weight % or more, more preferably 60 weight % or more, further preferably 70 weight % with On.In addition, seperation film can be substantially only made of thermoplastic resin (A).

As the concrete example of thermoplastic resin, can enumerate the polyolefin-based resins such as polyethylene, polypropylene, polymethylpentene, The polyester based resins such as polyethylene terephthalate, polybutylene terephthalate (PBT), polylactic acid, nylon 6, nylon66 fiber, Buddhist nun The propylene such as polyimides system resins, poly- (methyl) acrylate such as polyamide resins, polyetherimide, the polyimides such as dragon 11 Polyether systems resin, polyphenylene sulfide, polyether-ether-ketone, polysulfones, polyvinyl acetate, the celluloses such as acid system resin, polyacetals, polyphenylene oxide Ester etc..

Wherein, as thermoplastic resin of the invention, becoming good aspect in the through performance of water is preferably hydrophilic resin Rouge.

In the present invention, so-called thermoplastic resin refers to that the constituent of polymer includes hydrophilic group, also, the polymerization The epithelium of object and the contact angle of water are 90 ° of resins below, are more preferably 60 ° of hydrophilic resins below with the contact angle of water Rouge.Here so-called hydrophilic group is hydroxyl, carboxyl, carbonyl, amino, amide groups.

Seperation film can also include plasticizer (B), structure-forming agent (C) etc. other than thermoplastic resin (A).

It should be noted that seperation film can be wherein comprising liquid such as water in order to keep shape.However, in following theory In bright, for keeping these liquid of shape to consider not as the constituent element of seperation film.

(1-2) composition

< thermoplastic resin (A) >

As the concrete example of the thermoplastic resin (A) in the present invention, can be used for example, polyester, polyamide, polyacrylic acid Methyl esters, polyvinyl acetate, cellulose esters, polyester etc..Wherein, be preferably selected from polyester, polyamide, in cellulose esters at least 1 kind.

As the concrete example of cellulose esters, cellulose acetate, cellulose propionate, cellulose butyrate and cellulose can be enumerated Glucose unit present in the cellulose mixed esters etc. that has been blocked by two or more acyl group of 3 hydroxyls.It is mixed as cellulose The concrete example of ester can be enumerated for example, cellulose-acetate propionate, cellulose acetate-butyrate, acetate+lauric acid cellulose, acetic acid oleic acid Cellulose and acetic acid cellulose stearate etc..Each cellulose mixed esters illustrated has acetyl group and other acyl groups (for example, third Acyl group, bytyry, lauryl, oil base and stearyl etc.).Acetyl group and being averaged for other acyl groups in cellulose mixed esters take Dai Du preferably satisfies following formula.It should be noted that so-called average substitution degree, refers to present in every glucose unit of cellulose 3 hydroxyls in, acyl group has carried out chemically combined number.

1.0≤(average substitution degree of acetyl group+other acyl groups average substitution degree)≤3.0

0.1≤(average substitution degree of acetyl group)≤2.6

0.1≤(average substitution degrees of other acyl groups)≤2.6

By meeting above-mentioned formula, has separating property concurrently and diactinic film is achieved.Further, above-mentioned by meeting Formula, in the manufacture of seperation film, in melt spinning, the good thermal fluidity of resin combination is achieved.

Among the above, at least one kind of compound in cellulose-acetate propionate and cellulose acetate-butyrate is preferably comprised.It is logical It crosses and contains these cellulose esters, it is easy to accomplish the gap of the bent road rate with aftermentioned prescribed limit.

The weight average molecular weight (Mw) of cellulose esters in the present invention is preferably 5.0 ten thousand or more and 25.0 ten thousand or less.By making Weight average molecular weight (Mw) is 5.0 ten thousand or more, furthermore strong in the film of seperation film in terms of the thermal decomposition when that can inhibit melt spinning Degree is preferred in terms of can achieve realistic scale.By making weight average molecular weight (Mw) to be 25.0 ten thousand hereinafter, that can inhibit molten Melt-viscosity becomes excessively high, is preferred in terms of can carrying out stable melt spinning.

Weight average molecular weight (Mw) be more preferably 6.0 ten thousand or more and 22.0 ten thousand hereinafter, further preferably 8.0 ten thousand or more and 20.0 ten thousand or less.It should be noted that so-called weight average molecular weight (Mw), refers to the value calculated by GPC measurement, in embodiment It explains in detail.

As polyamide, can enumerate for example, by the ring-opening polymerisation of various lactams, various Diamines and various dicarboxyls The acquisitions such as the polycondensation of acids and the polycondensation of various aminocarboxylic acids various polyamide-based or by these ring-opening polymerisations and polycondensation Copolyamide class being combined with etc..As above-mentioned polyamide-based, copolyamide class, specifically, it can be cited for example that, Buddhist nun Imperial 6, nylon66 fiber, nylon 610, nylon 46, nylon 612, nylon 11, nylon 12, nylon 6/12 copolymer (epsilon-caprolactams and ten The copolymer of two lactams) and the nylon 6/66 copolymer (copolymerization of epsilon-caprolactams and 1,6- hexamethylene diamine/adipic acid nylon salt Object) etc. nylon, but not limited thereto.In addition it is also possible to which two or more is kneaded and uses by these polyamide.

In seperation film, as polyamide, it can only contain a kind of compound, two or more compound can also be contained.

In addition, seperation film preferably comprises especially nylon 6 and/or nylon among the above-mentioned polyamide as concrete example 66.By containing these polyamide, the seperation film with high separability energy is achieved.

The weight average molecular weight (Mw) of polyamide is preferably 10,000 or more and 1,000,000 or less.By making weight average molecular weight (Mw) be 10000 or more, in terms of the thermal decomposition when melt spinning can be inhibited, in addition, the film-strength in seperation film can achieve practical water Square face is preferred.It, can by making weight average molecular weight (Mw) to be 1,000,000 hereinafter, can inhibit the melt viscosity to become excessively high It is preferred in terms of carrying out stable melt spinning.Weight average molecular weight (Mw) is more preferably 20,000 or more and 900,000 hereinafter, further Preferably 30,000 or more and 800,000 or less.

Due to by the key that polymerization is formed being amido bond in polyamide, even if especially main in the case where being contacted with alkali The cutting of chain is also not susceptible to, therefore is preferred in terms of having good patience to alkali.

As polyester, can enumerate for example, having glycol moiety and polyester, the polymer in poly lactic acid series of dicarboxylic acid moiety etc.. In seperation film, as polyester, it can only contain a kind of compound, two or more compound can also be contained.

About the polyester with glycol moiety and dicarboxylic acid moiety, as glycol moiety, from the viewpoint of through performance, Preferably carbon atom number is 18 glycols below, and more preferably carbon atom number is 10 glycols below, further preferably Carbon atom number is 5 glycols below.From the durability improved to basic hydrolysis if the carbon atom number of glycol moiety is 2 or more From the viewpoint of be preferred.Specifically, can enumerate for example, ethylene glycol, 1,2-PD, 1,2- butanediol, 1,3- fourth two Alcohol, 1,4- butanediol, 2- methyl-1,3-propanediol, neopentyl glycol, 1,5- pentanediol, 1,6-HD, diethyl -1 2,2-, 3-propanediol, 2,2,4- trimethyl -1,3- pentanediol, 2- ethyl -1,3- hexylene glycol, 1,9- nonanediol, 1,10- decanediol, 2- The polyalkylenes such as aliphatic dihydroxy alcohols and dipropylene glycol such as butyl -2- ethyl -1,5- propylene glycol and 1,12- octacosanol Glycol etc..These glycols can be used alone, and also two or more kinds may be used.

As dicarboxylic acid moiety, can enumerate for example, terephthalic acid (TPA), M-phthalic acid, naphthalenedicarboxylic acid etc., do not limit especially It is fixed, it can be improved the crystallinity of resin if using terephthalic acid (TPA), therefore it is excellent, operational excellent to obtain mechanical property Different seperation film.It can inhibit excessive crystallization if using M-phthalic acid, therefore good permeability can be obtained Energy.Dicarboxylic acids can be used a kind, and also two or more kinds may be used, can there is no problem that ground plays effect of the invention.

In addition, seperation film preferably comprise among the above-mentioned polyester as concrete example especially polymer in poly lactic acid series and/ Or polyethylene terephthalate.By containing these polyester, the seperation film with high separability energy is achieved.

The weight average molecular weight (Mw) of polyester with glycol moiety and dicarboxylic acid moiety is preferably 1.0 ten thousand or more and 1,000,000 Below.By making weight average molecular weight (Mw) to be 1.0 ten thousand or more, in terms of the thermal decomposition when melt spinning can be inhibited, furthermore exist The film-strength of seperation film is preferred in terms of can achieve realistic scale.In addition, by make weight average molecular weight (Mw) be 1,000,000 with Under, melt viscosity can inhibited to become excessively high, be preferred in terms of stable melt spinning can be carried out.Weight average molecular weight (Mw) More preferably 20,000 or more and 900,000 hereinafter, further preferably 30,000 or more and 800,000 or less.

In seperation film of the invention, as thermoplastic resin (A), a kind of compound can be contained, can also containing 2 kinds with Upper compound.That is, seperation film contains at least one kind of compound in the thermoplastic resin for example enumerated in this specification.

In addition, seperation film of the invention, which is preferably comprised, is selected from cellulose among the above-mentioned thermoplastic resin as concrete example At least one kind of compound in ester, polyamide and polyester.

< plasticizer (B) >

Seperation film of the invention can contain plasticizer (B).Include in resin combination used in being film-made during fabrication In the case where plasticizer (B), by after thermoplastic resin (A) thermoplastification in the manufacture of film, plasticizer (B) can remain in separation In film, at least part plasticizer (B) can also be made to dissolve out from seperation film.In the case where dissolving out it, plasticizer is detached from Trace become the pore in film sometimes, as a result, through performance becomes more good.

The content of plasticizer (B) in seperation film is not particularly limited, for example, 40 weight % or less.Plasticizer (B) Content be more preferably 1 weight % or more and 35 weight % hereinafter, further preferably 3 weight % or more and 35 weight % hereinafter, Still more preferably for 5 weight % or more and 35 weight % are hereinafter, particularly preferably 10 weight % or more and 30 weight % or less.

The detailed content of plasticizer (B) is described below.

< structure-forming agent (C) >

Seperation film of the invention can contain structure-forming agent (C).

The content of structure-forming agent (C) in seperation film is preferably 5 weight % or more and 60 weight % or less.Structure is formed The content of agent (C) is more preferably 50 weight % or less.

Detailed content about structure-forming agent (C) is described below.

< antioxidant (D) >

Seperation film of the invention can contain antioxidant (D).It is particularly preferably anti-containing phosphorus system as antioxidant (D) Oxidant, particularly preferably pentaerythrite based compound.As pentaerythrite based compound, specifically, bis- (2,6- can be enumerated Di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphites etc..

In the case where containing phosphorous antioxidant, thermal decomposition when melt spinning is suppressed, and as a result, it is possible to improve film Intensity prevents the coloring to film.The content of antioxidant (D) is preferably 0.500 weight relative to the composition for carrying out melt spinning Measure % or less.

The shape of (1-3) seperation film

The shape of seperation film of the invention is not particularly limited, it is preferred to use the seperation film of macaroni yarn shape (hereinafter, " in Empty cortina ") or flat shape film (hereinafter, " flat membrane ").Wherein, hollow fiber membrane can efficiently be filled in component, can make Effective membrane area of the per unit volume of component is big, therefore is preferred.So-called hollow fiber membrane is that have hollow filiform Film.

From the viewpoint of improving through performance, the thickness of seperation film is preferably 1 μm or more and 1000 μm hereinafter, more excellent Be selected as 1 μm or more and 500 μm hereinafter, further preferably 2 μm or more and 400 μm hereinafter, particularly preferably 20 μm or more and 200 μm hereinafter, most preferably 50 μm or more and 150 μm or less.

In the case where hollow fiber membrane, from when making to be filled in component effective membrane area, examine with the viewpoint that film-strength has concurrently Consider, the outer diameter of hollow fiber membrane be preferably 50 μm or more and 5000 μm hereinafter, more preferably 100 μm or more and 5000 μm hereinafter, into One step be preferably 200 μm or more and 4000 μm hereinafter, particularly preferably 300 μm or more and 700 μm hereinafter, most preferably 400 μm Above and 700 μm or less.

In addition, in the case where hollow fiber membrane, according to the pressure drop for the fluid for flowing through hollow portion, with the relationship of lateral deflection pressure, The hollow rate of hollow fiber membrane be preferably 15% or more and 70% hereinafter, more preferably 20% or more and 65% hereinafter, further it is excellent It is selected as 25% or more and 60% or less.

The method of the outer diameter, hollow rate above range that make hollow fiber membrane is not particularly limited, such as can be by appropriate The shape of the tap of the spinning head of change manufacture macaroni yarn or can by the draw ratio that the winding speed/velocity of discharge calculates Lai Adjustment.

(1-4) co-continuous structure

Seperation film of the invention, which preferably comprises the phase of thermoplastic resin (A) and gap, has co-continuous structure.

About the composition of the phase containing thermoplastic resin, the explanation of the composition of seperation film is applied with respect to.

Here so-called co-continuous structure is micro- by transmission electron microscope (hereinafter, " TEM "), scanning electron When mirror (hereinafter, " SEM ") observes film section, the phase containing thermoplastic resin (A) and gap difference are continuous, and each other The state (referring to Fig.1) dimensionally to interweave.

The schematic diagram of co-continuous structure is (high such as " Port リ マ ー ア ロ イ basis と ying uses (second edition) (the 10.1st chapter) " Molecules can be compiled: the same people of Tokyo chemistry) in also recorded.

The width in so-called gap refers to the figure that will be observed by transmission electron microscope or scanning electron microscope It as carrying out Fourier transformation, maps using wave number as horizontal axis, by the longitudinal axis of intensity, is calculated by the wave number at the very big peak of resulting figure Period.

It is 1nm or more by the width in gap, good through performance can be played.The width in gap be preferably 2nm with On, more preferably 10nm or more, further preferably 20nm or more, particularly preferably 30nm or more.In addition, the width for passing through gap Degree is 1000nm hereinafter, the good separating property as seperation film can be played.The width in gap be preferably 600nm hereinafter, More preferably 200nm hereinafter, further preferably 100nm hereinafter, particularly preferably 80nm hereinafter, most preferably 50nm or less. In this specification, the width in gap is sometimes referred to simply as aperture.

In general, have the porous body of co-continuous structure compared with the porous body formed by the aggregate of particle, aperture Uniformity it is high.

What the uniformity in aperture can be drawn by the hole count of the pore using aperture as horizontal axis, to have the aperture as the longitudinal axis The half-peak breadth of curve judges.That is, curve forms sharp peak in the case where the film of uniform pore diameter, half-peak breadth narrows.It is another Aspect, in the non-uniform situation in aperture, curve forms wide peak, and half-peak breadth broadens.Should by using aperture as horizontal axis, with pore Number is that the uniform pore diameter that the half-peak breadth for the figure that the longitudinal axis is drawn carries out is evaluated even if using the inverse in aperture, i.e. wave number as horizontal axis It is able to carry out same evaluation, therefore uses and evaluates the figure that above-mentioned electron microscope image has carried out Fourier transformation.

Above-mentioned microscope figure seem using 10 times or more of the width in gap and 100 times of length below as side length just It is taken in rectangular visual field.In addition, making the horizontal axis wave number for having carried out the figure of Fourier transformation, makes longitudinal axis intensity, ask The half-peak breadth at the peak for the figure drawn out and the very big wave number at peak.

The tendency that the half-peak breadth at peak increases with the increase with the very big wave number at peak, therefore will be by the half-peak breadth at peak (a), the value for (a)/(b) that the very big wave number (b) at peak calculates is set as the index of the Evaluation for Uniformity in aperture.

For the stalling characteristic being excellent in, uniform pore diameter is preferably high, the value of above-mentioned (a)/(b) be preferably 1.5 hereinafter, More preferably 1.2 hereinafter, further preferably 1.0 or less.In addition, pore structure is more uniform from the viewpoint of separating property The more preferred, therefore the lower limit value of (a)/(b) is not particularly limited, but using the value for being greater than 0.

It should be noted that the detailed content of the measuring method in aperture is recorded in embodiment.

(1-5) song road rate

The bent road rate of seperation film of the invention is 1.0 or more and 6.0 or less.The bent road rate the low the more preferred, but theoretically 1.0 For lower limit.It is 6.0 hereinafter, the linearity of flow path improves by bent road rate, water penetration becomes good.Bent road rate be preferably 2.0 with It is upper and 6.0 hereinafter, more preferably 3.0 or more and 5.5 hereinafter, further preferably 3.0 or more and 4.5 or less.

The value for measuring and calculating under the conditions of the bent road rate recorded in the present specification is documented by the aftermentioned embodiment.

< percent opening >

The percent opening (hereinafter, " percent opening ") on the preferred surface of seperation film of the invention is 10% or more and 70% or less.It is logical Cross as 10% or more, can get good permeation flux, by for 70% hereinafter, can get good film-strength.More preferably 15% or more and 60% hereinafter, further preferably 20% or more and 50% hereinafter, still more preferably for 20% or more and 45% hereinafter, particularly preferably 20% or more and 40% hereinafter, most preferably 25% or more and 35% or less.

So-called percent opening is the area in the gap ratio shared in viewing area when having carried out observation to surface, by Area/the viewing area in voidage (%)=surface gap × 100 indicate.

The percent opening recorded in the present specification is using scanning electron microscope, documented by aftermentioned embodiment Under the conditions of measure and calculate value.

< film permeation flux >

The 50kPa of seperation film of the invention, the film permeation flux under the conditions of 25 DEG C are preferably 0.01m³/m²/ hr or more and 20m³/m²/ hr or less.Film permeation flux is more preferably 0.05m³/m²/ hr or more and 15m³/m²/ hr is hereinafter, further preferably 0.1m³/m²/ hr or more and 10m³/m²/ hr is hereinafter, particularly preferably 0.2m³/m²/ hr or more and 7m³/m²/ hr is hereinafter, most preferably For 0.5m³/m²/ hr or more and 5m³/m²/ hr or less.Width in gap is film infiltration in 1nm or more and 80nm situation below Saturating flux is preferably 0.70m³/m²/ hr or more and 20m³/m²/ hr is hereinafter, further preferably 0.75m³/m²/ hr or more and 15m³/m²/ hr or less.In the case where the width in gap is 80nm or more and 100nm situation below, film permeation flux is preferably 1.0m³/m²/ hr or more and 20m³/m²/ hr is hereinafter, preferably 1.1m³/m²/ hr or more and 15m³/m²/ hr or less.Width in gap Degree is in 100nm or more and 1000nm situation below, and film permeation flux is preferably 1.0m³/m²/ hr or more and 20m³/m²/hr Hereinafter, film permeation flux is more preferably 1.5m³/m²/ hr or more and 20m³/m²/ hr or less.The determination condition of film permeation flux exists It is described in detail in embodiment.

< additive >

Seperation film of the invention in the range that does not impair the effects of the present invention, can contain the addition other than above-mentioned substance Agent.As additive, can be used for example, organic lubricant, crystallization nucleating agent, organic filler, inorganic particulate, end-capping reagent, increasing It is chain agent, ultraviolet absorbing agent, infrared absorbent, coloring agent, delustering agent, antibacterial agent, antistatic agent, deodorant, fire-retardant Agent, weather resisting agent, antistatic agent, antioxidant, ion-exchanger, defoaming agent, coloring pigment, fluorescent whitening agent and dyestuff etc..

The purposes > of < seperation film

Seperation film of the invention is the film that can be especially used in water process.As water process film, specifically, can Enumerate microfiltration membranes and ultrafiltration membrane etc..Seperation film of the invention is particularly preferably suitable for ultrafiltration membrane.

< component >

Seperation film of the invention group can enter to separating film module when in use.Separating film module is for example with by more The perineurium and the shell for accommodating the perineurium that empty cortina is constituted.

In addition, if be flat membrane, then by being fixed on support or film is bonded each other and forms envelope shape film, further It is componentized as desired by collector pipe etc. is installed on.

2. manufacturing method

Next, about the method for manufacturing resin combination and seperation film of the invention, with resin combination and seperation film It is respectively specifically described in case where macaroni yarn and hollow fiber membrane, but not limited thereto.

As the manufacturing method of resin combination and seperation film of the invention, it is preferably applicable in melt spinning method.

So-called melt spinning method is the forming method of resin combination and film, with following processes: by leading to raw material Cross the process (resin melting process) that heating was melted and be kneaded and modulated molten resin；And next by the molten resin From the spinning head discharge of the slit-shaped as discharge mouth mold, cured process (molding procedure) is carried out by cooling.Melt spinning Method can also be suitable for the manufacture of any one of macaroni yarn and hollow fiber membrane.

As the raw material of resin combination and seperation film, above-mentioned thermoplastic resin (A), plasticizer (B), structure can be enumerated Forming agent (C), antioxidant (D).About respective concrete example, as described above.Above-mentioned raw materials are become to the fusing point of each raw material The mode of above temperature is heated, is melted, the tree using the progress melting mixing such as single screw extrusion machine, double screw extruder Oil/fat composition.

Especially the present invention provides a kind of manufacturing method of seperation film, and with following processes: resin melting process passes through Thermoplastic resin and structure-forming agent are melted and be kneaded and modulates molten resin；Molding procedure, by by above-mentioned melting Resin obtains membranaceous formed body from the discharge of discharge mouth mold；Co-continuous structure formation process, passes through thermotropic phase in formed body It separates and forms co-continuous structure；And dissolution process, it is formed and dissolving out structure-forming agent from above-mentioned resin combination Gap.

(resin melting process)

Resin melting process is the process for modulating molten resin used in melted masking.Comprising flat membrane in melted masking Form the formation with hollow fiber membrane.The formation of hollow fiber membrane is especially referred to as melt spinning.

[raw material]

The raw material (i.e. material used in resin melting process) of molten resin includes at least thermoplastic resin (A) and structure Forming agent (C) can further include plasticizer (B) and antioxidant (D).

About the example of thermoplastic resin (A), as described above.

The content of thermoplastic resin (A) in the total amount of raw material is 20 weight % or more and 90 weight % or less.By making The content of thermoplastic resin (A) is 20 weight % or more, be may be implemented with high-intensitive film.By making thermoplastic resin (A) Content be 90 weight % hereinafter, by plasticizer etc. addition carry out melt molding become easy, can assign good Stringiness.The content of thermoplastic resin (A) is more preferably 30 weight % or more and 85 weight % hereinafter, further preferably 40 weights Measure % or more and 80 weight % or less.

As plasticizer (B), as long as can be by thermoplastic resin (A) thermoplastification, that is, the compound melted, just without spy It does not limit.In addition, plasticizer (B) can be used alone or can be used together and uses two or more.As the plasticizer in the present invention (B), preferably polyalcohol based compound.As polyalcohol based compound, specifically, can enumerate for example, polyalkylene glycol, Glycerol based compound and caprolactone based compound or their derivative etc..

Wherein, due to showing thermoplastic a small amount of addition due to the good compatibility with thermoplastic resin (A) Property, therefore inhibit the reduction of the film-strength as caused by plasticizer, from this side considerations, preferably polyalkylene glycol.

As the concrete example of polyalkylene glycol, can enumerate for example, weight average molecular weight (Mw) be 200 or more and 2,000 with Under, polyethylene glycol (hereinafter, " PEG "), polypropylene glycol and polytetramethylene glycol etc..

The content of plasticizer (B) in the total amount of the raw material of molten resin be preferably 3 weight % or more and 50 weight % with Under.By making the 3 weight % of content or more of plasticizer (B), the thermoplasticity of thermoplastic resin (A) becomes good.By making to increase The content for moulding agent (B) is 50 weight % hereinafter, spinnability becomes good.The content of plasticizer (B) is more preferably 5 weight % or more And 40 weight % hereinafter, further preferably 7 weight % or more and 30 weight % or less.

Structure-forming agent (C) and can be used as long as mixture partially compatible with thermoplastic resin and its plasticizer The solvent dissolution of insoluble thermoplastic resin is decomposed.

So-called partially compatible is that two or more substance is fully compatible under the conditions of certain, but mutually separates under other circumstances.Knot Being configured to agent is in aftermentioned co-continuous structure formation process, and being placed under the conditions of specific temperature and thermoplastic resin The mutually substance of separation.Specific condition is aftermentioned.

As the concrete example of structure-forming agent (C), can enumerate for example, polyvinylpyrrolidone (hereinafter, " PVP "), PVP/ Vinyl acetate copolymer and PVP/ methylmethacrylate copolymer etc. include copolymer, polyvinyl alcohol or the Polyester of PVP Compound etc..They can be used alone or and with use.For PVP, in case of heat cross-linking then aftermentioned structure shape It is become difficult at the removing of agent (C), therefore it is preferable to use the less susceptible progress of intermolecular cross-linking, and can be molten crosslinking The smaller substance of the molecular weight below of molecular weight 20,000 out.Use the copolymerization of vinyl pyrrolidone and vinyl acetate etc. Object is also preferred in terms of inhibiting heat cross-linking.

The content of structure-forming agent (C) when melt spinning in the total amount of the raw material of molten resin is preferably 10 weight % Above and 60 weight % or less.By making the 10 weight % of content or more of structure-forming agent (C), thus aftermentioned co-continuous In structure formation process, thermoplastic resin lipid phase is mutually easily formed with 1nm or more and 1000nm week below with structure-forming agent The co-continuous structure of phase structure.By making the 60 weight % of content of structure-forming agent (C) hereinafter, resin combination can be inhibited In the excessive increase with the 1st phase partially compatible containing thermoplastic resin, the 2nd phase width.

In the total amount of the raw material of molten resin, the ratio of the total amount of plasticizer (B) and structure-forming agent (C) is preferably 13 weight % or more and 80 weight % or less.By make the 13 weight % of total amount of plasticizer (B) and structure-forming agent (C) with On, it can get good stringiness and co-continuous structure.By the total amount 80 for making plasticizer (B) and structure-forming agent (C) Weight % is hereinafter, can get the resin combination and seperation film of good intensity.The conjunction of plasticizer (B) and structure-forming agent (C) Metering be more preferably 20 weight % or more and 70 weight % hereinafter, further preferably 30 weight % or more and 60 weight % with Under.

Inhibit the excessive increase of the thickness of the phase with structure-forming agent in resin combination also to have and inhibits seperation film Gap width the effect excessively increased, separating property becomes good.The content of structure-forming agent (C) is more preferably 15 weights % or more and 55 weight % are measured hereinafter, further preferably 20 weight % or more and 50 weight % or less.

The content of antioxidant (D) in the total amount of the raw material of seperation film is preferred relative to the composition for carrying out melt spinning For 0.005 weight % or more and 0.500 weight % or less.

Containing ratio by molten resin without solvent or solvent is 20 weight % hereinafter, in aftermentioned molding work Component fluctuation after sequence also not as a whole, therefore in aftermentioned co-continuous structure formation process, it is carried out by heat treatment Hole appearance at becoming easy.

(molding procedure)

Molding procedure is the process that molten resin is shaped to shape desired by hollow Filamentous or flat membrane shape etc..It will pass through The molten resin of molding procedure is known as " formed body ".

By melt spinning method that molten resin progress by above-mentioned modulation, containing thermoplastic resin (A) is hollow In the case where threading, spinning temperature (temperature of filament spinning component) be preferably (Tm+5 DEG C) more than and (Tm+50 DEG C) below.Tm is should Crystalline melting temperature in the heating measurement using differential scanning calorimetry (DSC) (DSC) of molten resin.The determination condition of DSC is in reality It applies in example and is described in detail.

Spinning temperature is more preferably (Tm+5 DEG C) or more and (Tm+40 DEG C) hereinafter, further preferably more than (Tm+5 DEG C) And (Tm+30 DEG C) is below.By inhibiting the spinning temperature than usually low, so that resin combination and separation film strength become Get Geng Gao.

In the modulation of the formed body of hollow filiform, spinning head can be used as discharge mouth mold.Specifically, can make With the spinning head of c-type slit, multiple (2~5) arcuations (arc shape) of configuration slit portion and formed 1 tap spinning head, The spinning head etc. of pipe sleeve (tube-in-orifice) type.

Molten resin squeezes out downwards from the tap of the spinning head for the lower part for being installed on filament spinning component.Here, from spinneret The distance H of lower surface to cooling device (ventilator) upper end of head be preferably 0mm or more and 500mm hereinafter, more preferably 0mm with Upper and 400mm is hereinafter, further preferably 0mm or more and 300mm or less.

When the macaroni yarn that will be discharged from spinning head is cooling, the temperature of the cooling wind of cooling device (ventilator) is preferably 5 DEG C or more and 80 DEG C or less.In addition, the wind speed of cooling wind is preferably 0.1m/ seconds or more and 2.0m/ second hereinafter, more preferably 0.3m/ seconds or more and 2.0m/ second hereinafter, further preferably 0.5m/ seconds or more and 2.0m/ seconds or less.

It is wound by the macaroni yarn that cooling device is cooled by winding device.It can be by winding speed/velocity of discharge The draw ratio of calculating is preferably 1 or more and 1, and 000 hereinafter, more preferably 20 or more and 900 hereinafter, further preferably 30 or more And 800 or less.

(co-continuous structure formation process)

Co-continuous structure formation process carries out after molding procedure.

In order to form co-continuous structure, that is, the 1st phase containing thermoplastic resin and the 2nd phase point with the 1st phase partially compatible Structure that is not continuous and being interlaced with one another, can use and mutually separate.Mutually separation is compatible with structure-forming agent by thermoplastic resin The temperature of composition become being induced in particular range.It is induced under the conditions of by temperature in this way in particular range Mutually separation is known as Thermal inactive.As the temperature in particular range, preferably spinodal (spinodal line) below and Temperature more than glass transition temperature.

That is, co-continuous structure formation process is implemented and the temperature specific range for making formed body.Temperature range is excellent Be selected as 40 DEG C or more and 250 DEG C hereinafter, more preferably 50 DEG C or more and 220 DEG C hereinafter, further preferably 60 DEG C or more and 200 DEG C hereinafter, particularly preferably 70 DEG C or more and 180 DEG C or less.When being set as specific temperature range, by using liquid conduct Heating agent can get the low structure of song road rate.Here the so-called liquid used as heating agent, is not particularly limited, specifically, can Water, silicone oil, N-Methyl pyrrolidone (hereinafter, " NMP "), atoleine, PEG, polymer melt etc. are illustrated, wherein it is preferred that making With the high liquid of the boiling points such as silicone oil, atoleine, PEG, polymer melt.It should be noted that thinking co-continuous formation work The temperature of formed body in sequence and the temperature of heating agent are identical.Therefore, the temperature range of above-mentioned formed body is also applied for heating agent Temperature range.

In order to obtain co-continuous structure, particularly preferably using the mutually separation carried out by spinodal decomposition.It is preferred that being total to Thermoplastic resin is temporarily compatible before mutually separating with structure-forming agent when continuous structure, by the phase point carried out by spinodal decomposition From and form structure.In this way, can get the resin combination that the 2nd phase has clean width.

(dissolution process)

After co-continuous structure formation process, by the way that at least part of the 2nd phase is removed (dissolution), sky can be formed Gap.

The removing of 2nd phase, for example, by insoluble or not decomposition heat plastic resin (A), and can dissolve or decompose knot Dip forming body is configured in the solvent of agent to carry out.Such processing is known as dissolution process.

As the solvent in dissolution process, can illustrate for example, acidic aqueous solution, alkaline aqueous solution, water, alcohol and alcohol are water-soluble Liquid etc..

It is preferred that making the surface of film for example, by the aqueous solution containing alcohol and alkaline aqueous solution etc. before sky cortina in use Hydrophiling.

In this way, can manufacture with the phase containing thermoplastic resin and the gap with defined width and there is regulation Bent road rate seperation film of the invention.

Embodiment

Embodiment described below further specifically describes the present invention, but the present invention is not by these embodiment any restrictions.

[measurement and evaluation method]

Each characteristic value in embodiment is found out by the following method.

(1) average substitution degree of cellulose esters

The calculation method of the average substitution degree of the cellulose esters combined about acetyl group and acyl group and cellulose, following institute It states.

8 hours cellulose esters 0.9g have been dried in weighing at 80 DEG C, and acetone 35mL and dimethyl sulfoxide 15mL is added and carries out After dissolution, acetone 50mL is further added.0.5N- sodium hydrate aqueous solution 30mL is added while stirring, is saponified 2 hours. Hot water 50mL is added, after the washing of flask side, is titrated using phenolphthalein as indicator with 0.5N- sulfuric acid.Additionally by with sample Same procedure has carried out empty test.The supernatant of solution after titration is diluted to 100 times, using ion chromatograph, is surveyed The composition of organic acid is determined.By measurement result and the sour composition analysis based on ion chromatograph as a result, being taken by following formula calculating Dai Du.

TA=(B-A) × F/ (1000 × W)

DSace=(162.14 × TA)/[{ 1- (Mwace- (16.00+1.01)) × TA }+{ 1- (Mwacy- (16.00+ 1.01))×TA}×(Acy/Ace)]

DSacy=DSace × (Acy/Ace)

TA: whole organic acid contents (mL)

A: sample titer (mL)

B: sky test titer (mL)

F: the potency of sulfuric acid

W: sample weight (g)

DSace: the average substitution degree of acetyl group

DSacy: the average substitution degree of acyl group

Mwace: the molecular weight of acetic acid

Mwacy: the molecular weight of other organic acids

Acy/Ace: the molar ratio of acetic acid (Ace) and other organic acids (Acy)

162.14: the molecular weight of the repetitive unit of cellulose

16.00: the atomic weight of oxygen

1.01: the atomic weight of hydrogen

(2) weight average molecular weight (Mw) of thermoplastic resin

It is made it completely dissolved in such a way that the concentration of thermoplastic resin becomes 0.15 weight % in tetrahydrofuran or NMP, system At GPC measurement sample.Using the sample, under the following conditions, GPC measurement is carried out by Waters2690, passes through polyphenyl second Alkene conversion finds out weight average molecular weight (Mw).

Column: by 2 Dong ソ ー TSK gel GMHHR-H connections

Detector: Waters2410 differential refractometer RI

Mobile phase solvent: tetrahydrofuran or NMP

Flow velocity: 1.0mL/ minutes

Sample volume: 200 μ L

(3) outer diameter (μm) of hollow fiber membrane

Pass through the thickness in the optical microscopy pair direction vertical with the length direction of hollow fiber membrane (fibre diameter direction) and film The section in degree direction is observed, is shot, and the outer diameter (μm) of hollow fiber membrane is calculated.It should be noted that the outer diameter of hollow fiber membrane It is calculated using 10 hollow fiber membranes, is set as its average value.

It it should be noted that macaroni yarn is formed body, and is also resin combination, therefore below sometimes claim macaroni yarn For " resin combination ".

(4) thickness of hollow fiber membrane

It observed, shot by section of the optical microscopy to the fibre diameter direction of hollow fiber membrane, to 1 macaroni yarn Film determines the thickness of 6 positions.The measurement is carried out to 10 hollow fiber membranes, is averaged and is set as the thickness of hollow fiber membrane.

(5) hollow rate (%) of hollow fiber membrane

It observed, shot by section of the optical microscopy to the fibre diameter direction of hollow fiber membrane, measure section The area Sb of gross area Sa and hollow portion, are calculated using following formula.It should be noted that hollow rate is calculated using 10 hollow fiber membranes Out, it is set as its average value.

Hollow rate (%)=(Sb/Sa) × 100

(6) width (nm) in the gap in seperation film

Pre-treatment (TEM): ultra-thin section is cut out along the direction vertical with the length direction of seperation film.

Pre-treatment (SEM): by that will implement after dissolving out the seperation film liquid nitrogen frozen that process obtains, to be formed and be separated The mode in the section in the vertical direction of the length direction of film applies stress and cuts off, and is sputtered by platinum.

Observation: using TEM or SEM with the length direction of multiplying power 10,000 or more and 100,000 or less observation and seperation film The section in vertical direction obtains the image of 1 visual field.It should be noted that small with that cannot be observed with SEM in gap It is observed in the case where width by TEM.The image that square is cut out from resulting image, has carried out Fourier transformation Afterwards, using wave number as horizontal axis, using intensity as longitudinal axis drafting figure.The period is calculated from the wave number at very big peak, which is set as the visual field Gap width.Suitably observation multiplying power is adjusted in the case where cannot get very big peak and is observed again, and the width in gap is carried out Calculating.In the case where the side length of the width in resulting gap and the image of above-mentioned square is unsatisfactory for the relationship of formula (2), Change the size of above-mentioned square and calculate the width in gap, is adjusted in a manner of meeting the relationship of formula (2).It needs to illustrate It is that observation position includes, along film thickness direction to take 10 positions at equal intervals, to calculate gap in each observation position near two surfaces Width.Width using the numerical value of the smallest observation position of the width in gap therein as gap.

Width × 10 in gap≤square side length≤gap width × 100 formulas (2)

(7) through performance (film permeation flux (m³/m²/h))

Measure the transmission water for conveying 30 minutes distilled water under conditions of 25 DEG C of temperature, filtering differential pressure 50kPa and obtaining (m³), it is converted into (h) per unit time and per membrane area (m²) numerical value, be set as the through performance (unit=m of pure water³/m²/ h).It should be noted that make in embodiment the compact package of the effective length 200mm formed by 4 hollow fiber membranes and with Inner pressed has carried out film filtration treatment.Therefore per membrane area is calculated by the effective length of mean inside diameter and hollow fiber membrane.

(8) calculating of the very big wave number (b) in half-peak breadth (a)/peak

Using TEM or SEM, with 10,000 times of multiplying power or more and 200,000 times or less to resin combination or and seperation film The section in the vertical direction of length direction observed and obtain image.Resulting image is become with the side length of square 10 times or more of the width in the gap of the width or seperation film of the 2nd phase of resin combination and 100 times of modes below select to fit When range carries out Fourier transformation, using wave number as horizontal axis, using intensity as longitudinal axis drafting figure.It is found out by the spike number and half-peak breadth of figure (a)/(b) as average pore size and the index of uniformity.

(9) crystalline melting temperature (DEG C) of molten resin

Substance obtained by above-mentioned molten resin quenching, solidification will be made as sample, use セ イ コ ー イ Application ス Star Le メ Application Star (strain) differential scanning calorimetry (DSC) DSC-6200 processed will carry out 25 DEG C, 8 hours vacuum drying sample about 5mg are placed in In aluminum trays, heated up after 350 DEG C with 20 DEG C/min from -50 DEG C of heating rate, melting keeps 5 in the state of 350 DEG C Minute, the crystalline melting peak observed at this time is set as crystalline melting temperature (DEG C).It should be noted that there are multiple crystallizations In the case where melting peak, using the crystalline melting peak occurred in highest temperature side.

(10) percent opening (%)

After being sputtered with platinum and implemented the pre-treatment of seperation film, using scanning electron microscope with multiplying power 10,000 Times or more and 200,000 times or less observation separation membrane surface obtains image.Resulting image is being cut out into 1 μm of side length just It is rectangular, binaryzation and areal calculation are carried out using image analysis software, determines the area in gap.Percent opening is found out by formula (3).

Percent opening=gap area/viewing area × 100 formulas (3)

(11) bent road rate (-)

The bent road rate of hollow fiber membrane is calculated by following formula (4).

Here, V_P: pore specific volume (m³/ g), S_BET: specific surface area (m²/ g), ε: voidage (-), k: transmission coefficient (m²)。

V_P/S_BETIt can be by utilizing BET determination of adsorption method V_PAnd S_BETTo calculate.BET determining adsorption has used BELSORP- Mini II (マ イ Network ロ ト ラ ッ Network ベ Le Co., Ltd.).

Voidage ε is calculated by following formula (5).

ε=1-w/ ((R_o ²-R_i ²) × π × I × ρ) formula (5)

Here, w: dry weight (g), R_oThe outer diameter (m) of hollow fiber membrane, R_iThe internal diameter (m) of hollow fiber membrane, π: pi, l: Film length (m), ρ: the density (g/m of thermoplastic resin³)。

It should be noted that k is calculated by following formulas (6).

K=(Q × R_i×π·I×μ×In(R_o/R_i))/(2π×I×P)···(6)

Here, Q: film permeation flux (m³/m²/ s), μ: the viscosity (Pas) of water, R_o: the outer diameter (m) of hollow fiber membrane, R_i: The internal diameter (m) of hollow fiber membrane, π: pi, 1: film length (m) P (Pa): applies pressure.

[thermoplastic resin (A)]

Cellulose esters (A1): cellulose-acetate propionate

240 parts by weight of acetic acid and 67 parts by weight of propionic acid are added in 100 parts by weight of cellulose (cotton linters), are mixed at 50 DEG C It closes 30 minutes.Mixture is cooling after room temperature, 172 weight of acetic anhydride cooled in ice bath as esterifying agent is added Part and 168 parts by weight of propionic andydride stir within 150 minutes as 4 parts by weight of sulfuric acid of esterification catalyst, and it is anti-to have carried out esterification It answers.In the esterification reaction, when more than 40 DEG C, water-bath cooling is used.After the reaction, through addition in 20 minutes as reaction stopping agent The mixed solution of 33 parts by weight of 100 parts by weight of acetic acid and water hydrolyzes superfluous acid anhydride.Then, 333 parts by weight of acetic acid and water is added 100 parts by weight, heating stirring 1 hour at 80 DEG C.After the completion of reaction, the aqueous solution comprising 6 parts by weight of sodium carbonate is added, it will The cellulose-acetate propionate of precipitation is separated by filtration, 4 hours dry at 60 DEG C after being then washed with water, and obtains cellulose esters (A1) (cellulose-acetate propionate).The acetyl group of resulting cellulose-acetate propionate and the average substitution degree of propiono are respectively 1.9,0.7, weight average molecular weight (Mw) is 17.8 ten thousand.

Polyamide (A2): nylon66 fiber (eastern レ (strain) society nylon 66 resin " ア ミ ラ Application " (registered trademark))

Polyamide (A3): nylon 6 (eastern レ (strain) society nylon 6 resin " ア ミ ラ Application " (registered trademark))

Plasticizer (B)

Plasticizer (B1): PEG, weight average molecular weight (Mw) 600

Structure-forming agent (C)

Structure-forming agent (C1): PVP (K17)

Structure-forming agent (C2): PVP/ vinyl acetate copolymer ((the BASF ジ ャ パ Application strain formula meeting of Kollidon VA 64 Society))

Antioxidant (D)

Antioxidant (D1): bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphites

Antioxidant (D2): hindered phenolic antioxidant ((BASF (strain) society of イ Le ガ ノ ッ Network ス (registered trademark) 1098 System))

[manufacture of resin combination and seperation film]

(embodiment 1)

By 57.3 weight % of cellulose esters (A1), as plasticizer (B) weight average molecular weight (Mw) 600 PEG (B1) (three Foreignize into Industrial Co., Ltd) 12.6 weight %, PVP (K17) (C1) (BASF ジ ャ パ Application Co., Ltd.) 30.0 weight % and Bis- 0.1 weight % of (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphites (D1) as antioxidant (D) Using double screw extruder at 240 DEG C melting mixing, pelletize after being homogenized, obtain the tree of melt spinning Rouge.The resin has been carried out 80 DEG C, 8 hours to be dried in vacuo.

The resin dried is supplied to double screw extruder and is melted at 230 DEG C, is kneaded and melting tree is made Rouge (resin melting process).Molten resin is imported to the fused spinning assembling parts that spinning temperature is 230 DEG C, at discharge rate 10g/ points Under conditions of clock, from the outside of the mouth mold with 1 hole (pore radius 4.6mm, slit width 0.43mm is discharged in dual tubular type) Annulus spins downwards (molding procedure).By the spun macaroni yarn from the lower surface of mouth mold to cooling device (ventilator) The distance H of upper end becomes the mode Directed cooling device of 150mm, passes through the cooling air cooling of 25 DEG C, wind speed 1.5m/ seconds on one side, After being wound in such a way that draw ratio becomes 200 with up- coiler on one side, macaroni yarn is heated 20 minutes in 180 DEG C of PEG.

Resulting resin combination is immersed in 50% ethanol water 12 hours, thus dissolution structure-forming agent and It is interstitial while implementing hydrophiling.Using the macaroni yarn Jing Guo alcohol treatment as " seperation film ", physical property is determined.It will knot Fruit is shown in Table 1.

(embodiment 2~11, comparative example 1)

The composition of melt spinning resin combination, manufacturing condition are changed as table 1 or 2 respectively, in addition to this, with Embodiment 1 operates in the same way and obtains seperation film.By the physical property of resulting seperation film it is shown in table 1 or 2 in.

(embodiment 12)

By 52.3 weight % of polyamide (A2), 7.2 weight % of plasticizer (B1), 40.0 weight % of structure-forming agent (C2), 0.5 weight % of antioxidant (D2) utilizes double screw extruder melting mixing at 260 DEG C, is made after being homogenized Grain, obtains the resin of melt spinning.The resin has been carried out 80 DEG C, 8 hours to be dried in vacuo.

The resin dried is supplied to double screw extruder and is melted at 240 DEG C, is kneaded and melting tree is made Rouge (resin melting process).Molten resin is imported to the fused spinning assembling parts that spinning temperature is 220 DEG C, at discharge rate 10g/ points Under conditions of clock, from the outside of the mouth mold with 1 hole (pore radius 4.6mm, slit width 0.43mm is discharged in dual tubular type) Annulus spins downwards (molding procedure).By the spun macaroni yarn from the lower surface of mouth mold to cooling device (ventilator) The distance H of upper end becomes the mode Directed cooling device of 150mm, passes through the cooling air cooling of 25 DEG C, wind speed 1.5m/ seconds on one side, After being wound in such a way that draw ratio becomes 400 with up- coiler on one side, macaroni yarn is heated 10 minutes in 180 DEG C of PEG.

Resulting resin combination is immersed in 50% ethanol water 12 hours, thus dissolution structure-forming agent and It is interstitial while implementing hydrophiling.Macaroni yarn Jing Guo alcohol treatment is set as " seperation film ", determines physical property.It will knot Fruit is shown in Table 2.

(embodiment 13)

The manufacturing condition of melt spinning resin combination is changed as table 2 respectively, in addition to this, with embodiment 12 It operates in the same way and obtains seperation film.The physical property of resulting seperation film is shown in Table 2.

(embodiment 14)

By 52.3 weight % of polyamide (A3), 7.2 weight % of plasticizer (B1), 40.0 weight % of structure-forming agent (C2), 0.5 weight % of antioxidant (D2) utilizes double screw extruder melting mixing at 260 DEG C, is made after being homogenized Grain, obtains the resin of melt spinning.The resin has been carried out 80 DEG C, 8 hours to be dried in vacuo.

The resin dried is supplied to double screw extruder and is melted at 240 DEG C, is kneaded and melting tree is made Rouge (resin melting process).Molten resin is imported to the fused spinning assembling parts that spinning temperature is 220 DEG C, at discharge rate 10g/ points Under conditions of clock, from the outside of the mouth mold with 1 hole (pore radius 4.6mm, slit width 0.43mm is discharged in dual tubular type) Annulus spins downwards (molding procedure).By the spun macaroni yarn from the lower surface of mouth mold to cooling device (ventilator) The distance H of upper end becomes the mode Directed cooling device of 150mm, passes through the cooling air cooling of 25 DEG C, wind speed 1.5m/ seconds on one side, After being wound in such a way that draw ratio becomes 400 with up- coiler on one side, macaroni yarn is heated 10 minutes in 180 DEG C of PEG.

Resulting resin combination is immersed in 50% ethanol water 12 hours, thus dissolution structure-forming agent and It is interstitial while implementing hydrophiling.Macaroni yarn Jing Guo alcohol treatment is set as " seperation film ", determines physical property.It will knot Fruit is shown in Table 2.

(comparative example 2)

By 71.0 weight % of cellulose esters (A1), as plasticizer (B) weight average molecular weight 600 polyethylene glycol (B1) (Sanyo Chemical Industries, Ltd.) 20.0 weight %, PVP (K17) (C1) (the BASF ジ ャ パ Application as structure-forming agent (B) Co., Ltd.) 8.9 weight % and bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythrites two as antioxidant (D) it is sub- 0.1 weight % of phosphate (D1) utilizes double screw extruder melting mixing at 240 DEG C, pelletizes after being homogenized, Obtain the resin of melt spinning.The resin has been carried out 80 DEG C, 8 hours to be dried in vacuo.

The resin dried is supplied to double screw extruder and is melted at 230 DEG C, is kneaded and melting tree is made Rouge (resin melting process).Molten resin is imported to the fused spinning assembling parts that spinning temperature is 200 DEG C, at discharge rate 10g/ points Under conditions of clock, from the mouth mold with 4 mouth die holes (pore radius 4.6mm, slit width 0.43mm is discharged in dual tubular type) Outside annulus spins downwards (molding procedure).By the spun macaroni yarn with (logical from the lower surface of mouth mold to cooling device Air duct) upper end distance H become 150mm mode Directed cooling device, on one side pass through 0.5m/ seconds 25 DEG C, wind speed cooling winds And cool down, (co-continuous structure formation process) is wound with up- coiler in such a way that draw ratio becomes 200 on one side.By what is be achieved in that The physical property of macaroni yarn (resin combination) is shown in Table 2.

Resulting resin combination is immersed in 50% ethanol water 12 hours, thus dissolution structure-forming agent and It is interstitial while implementing hydrophiling.Macaroni yarn Jing Guo alcohol treatment is set as " seperation film ", determines physical property.It will knot Fruit is shown in Table 2.

(comparative example 3)

The composition of melt spinning resin combination, manufacturing condition are changed as table 2 respectively, in addition to this, with reality Example 2 is applied to operate in the same way and obtain macaroni yarn (resin combination) and seperation film.By the object of resulting macaroni yarn and seperation film Property is shown in Table 2.

[table 1]

[table 2]

The film of embodiment 1~14 all has co-continuous structure.Further, according to Tables 1 and 2 as a result, embodiment 1~14 Seperation film bent road rate all in 1.0 or more and 6.0 ranges below, further, (a)/(b) (hollow fiber membrane) be 1.50 with Under, the even width in gap.

In the seperation film of comparative example 1, although being porous body, co-continuous structure, film permeation flux cannot be confirmed It is 0, bent road rate can not be calculated.About comparative example 2, although the width in gap is in 1nm or more and 80nm range below and has Co-continuous structure, but bent road rate is more than 6, film permeation flux is less than 0.7.About comparative example 3, although the width in gap is in 80nm Above and 100nm range below and there is co-continuous structure, but bent road rate is more than 6, film permeation flux is less than 1.0.Qu Lu The low film of rate shows the high water permeability of the film with width and film thickness than the gap with equal extent.

Using specific scheme to the detailed description of the invention, but can be without departing substantially from the intent and scope of the present invention the case where Under make various changes and deform that it would have been obvious for a person skilled in the art.

Industry utilizability

The present invention is separating property and through performance is excellent, seperation film that mainly formed by cellulose-based resin.This hair Bright seperation film can be used for the water process film from the process industries such as seawater, salt water, sewage, draining water, drinking water etc., people The medical film of work kidney, blood plasma separation etc., the industrial film of food/beverage of concentration of juices etc., separation exhaust gas, titanium dioxide Used in electronic industry film such as gas separation membrane, fuel cell separator plate of carbon etc. etc..As the type of above-mentioned water process film, Ke Yiyou It is selected to microfiltration membranes, ultrafiltration membrane etc..

It is described in detail by the present invention referring to specific embodiment, but can be without departing from the spirit and scope of the present invention In the case where be added it is various change, amendment it would have been obvious for a person skilled in the art.

The application is based on Japanese patent application (Patent 2017-67096), content conduct filed on March 30th, 2017 Referring to and be introduced into herein.

Claims (14)

1. a kind of seperation film, containing thermoplastic resin,

The seperation film has width for 1nm or more and the gap below 1000nm,

The bent road rate in the gap is 1.0 or more and 6.0 or less.

2. seperation film according to claim 1 has and is formed by the phase containing the thermoplastic resin and the gap Co-continuous structure.

3. seperation film according to claim 1 or 2 is in the horizontal axis for carrying out Fourier transformation to MIcrosope image and obtaining In the curve of wave number, the longitudinal axis for the figure of intensity, when being set as (a) by half-peak breadth, the very big wave number at peak be set as (b), the separation Film includes the region of 0 < (a)/(b)≤1.5, and the microscope figure seems with the width in the gap of the seperation film The MIcrosope image that 10 times or more and 100 times of length below take in the visual field as the square of side length.

4. seperation film described in any one of claim 1 to 3,50kPa, the film permeation flux under the conditions of 25 DEG C are 0.05m³/m²/ h or more and 20m³/m²/ h or less.

5. seperation film according to any one of claims 1 to 4, the seperation film with a thickness of 1 μm or more and 1000 μm Below.

6. seperation film according to any one of claims 1 to 5, the seperation film is macaroni yarn shape.

7. seperation film according to claim 6, the outer diameter of the macaroni yarn shape is 100 μm or more and 5000 μm or less.

8. seperation film according to any one of claims 1 to 7, the thermoplastic resin includes selected from cellulose esters, gathers At least one kind of compound in amide and polyester.

9. seperation film according to claim 8, the cellulose esters is cellulose-acetate propionate and/or cellulose acetate butyrate Element.

10. seperation film according to claim 8, the polyamide is nylon 6 and/or nylon66 fiber.

11. seperation film according to claim 8, the polyester is polymer in poly lactic acid series and/or poly terephthalic acid second Diol ester.

12. a kind of manufacturing method of seperation film, with following processes:

Resin melting process, by by 20 weight % or more and 90 weight % thermoplastic resin below and 10 weight % or more And 60 weight % structure-forming agent below melted and be kneaded and modulate molten resin；

Molding procedure obtains membranaceous formed body and the molten resin is discharged from discharge mouth mold；

Co-continuous structure formation process passes through 40 DEG C or more and 220 DEG C of liquid below in the molten resin or formed body In Thermal inactive, formed and formed by the 1st phase containing thermoplastic resin and with the 2nd phase of the 1st phase partially compatible Co-continuous structure；And

Process is dissolved out, by the way that after the co-continuous structure formation process and molding procedure, the 2nd phase is dissolved out from the formed body And form gap.

13. the manufacturing method of seperation film according to claim 12, the thermoplastic resin is cellulose esters.

14. the manufacturing method of seperation film according to claim 12 or 13, in the molding procedure, by using spinneret Head forms macaroni yarn as the discharge mouth mold.